CN117323974A - 一种聚苯胺改性亲水纳米空心微囊制备方法 - Google Patents
一种聚苯胺改性亲水纳米空心微囊制备方法 Download PDFInfo
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明属于二氧化碳捕获技术领域,具体涉及一种聚苯胺改性亲水纳米空心微囊制备方法,具体工艺过程包括制备超交联空心微囊(HCP‑HC)、制备磺酸化HCP‑HC(S‑HCP‑HC)和制备PAN改性S‑HCP‑HC(PANI@S‑HCP‑HC)共三个步骤,基于聚苯胺本身具有的导电性使复合材料具有电化学活性,S‑HCP‑HC具有的亲水、结构可调、比表面积大、稳定性好、结构多样、价格便宜、可以负载其它金属等优点,将PANI与磺化后的HCP‑HC结合,S‑HCP‑HC的亲水性使PANI进入到S‑HCP‑HC的孔结构中,使PANI@S‑HCP‑HC具有良好的形貌,并保持高比表面积;其原理科学可靠,工序操作简单,反应条件温和,无需特殊的反应设备和需昂贵的催化剂,生产成本低廉。
Description
技术领域:
本发明属于二氧化碳捕获技术领域,具体涉及一种聚苯胺改性亲水纳米空心微囊制备方法,以制备碳捕获电极,用于CO2的电化学捕获。
背景技术:
随着工业化程度的加深,大气中温室气体的浓度不断上升,尤其是CO2,全球气候变暖,使得极端天气增加,能源危机等问题的出现推动着人们对二氧化碳转化的研究。碳捕获和利用的总体战略旨在将二氧化碳转化为有经济价值的化学品后回收,对于保护地球生态环境、促进人类社会可持续发展具有十分重要的意义。
目前,空心有机微孔微囊在催化,电化学,医学领域中得到了广泛的应用。例如,中国专利201310371108.7公开的一种基于聚乙二醇及叶酸接枝的聚乙烯亚胺改性的PLGA载药空心微囊的制备方法,包括:(1)将叶酸FA溶于溶剂中,加入N-羟基琥珀酰亚胺NHS及碳二亚胺EDC,再加入氨基聚乙二醇羧酸NH2-PEG-COOH,然后在25-28℃条件下,搅拌反应2-3d,透析,冻干,再复溶于溶剂中,加入N-羟基琥珀酰亚胺NHS和碳二亚胺EDC,再加入聚乙烯亚胺PEI,在25-28℃条件下,搅拌反应2-3d,透析,冻干,得到PEI-PEG-FA聚合物;(2)将聚乳酸羟基乙酸共聚物PLGA溶于有机溶剂中得到油相;将盐酸阿霉素DOX·HCl溶于超纯水中,得到水相;然后将油相和水相混合,在冰水浴中超声处理20-30s,得到油包水W/O乳液;(3)将上述W/O乳液加入聚乙烯醇PVA水溶液中,冰水浴条件下进行均质化,得到水包油包水W/O/W乳液;(4)将上述W/O/W乳液加入异丙醇水溶液中,搅拌1-4h,离心洗涤,得到PLGA-DOX载药空心微囊;(5)将上述PLGA-DOX载药空心微囊分散于水中,加入PEI-PEG-FA聚合物水溶液,搅拌15-30min,离心洗涤,分散在水中,冷冻干燥,得到具有良好的药物缓释性能,肿瘤细胞靶向治疗效果的基于聚乙二醇及叶酸接枝的聚乙烯亚胺改性的PLGA载药空心微囊,为多功能靶向药物制剂的开发提供了借鉴。中国专利201210549671.4公开的一种多孔聚合物空心微囊,按以下方法制备的产物:步骤一:将纳米二氧化硅颗粒加入无水乙醇中,超声分散,并加入氨水,然后加入硅烷偶联剂3-(甲基丙烯酰氧)丙基三甲氧基硅烷得到混合液,搅拌12~36小时进行纳米二氧化硅颗粒表面改性,将混合液离心,倒掉上层清液,使用无水乙醇或甲醇洗涤3~5次,得到表面改性的纳米二氧化硅颗粒;步骤二:将表面改性的纳米二氧化硅颗粒超声分散于无水乙醇,随后加入十二烷基苯磺酸钠、碳酸氢钠和水,超声搅拌30~90分钟,再加入单体苯乙烯和共聚单体二乙烯基苯得到混合液,在40~60℃下搅拌30~90分钟,升温至70~90℃,加入引发剂搅拌1~5小时,将混合液离心,倒掉上层清液,使用无水乙醇或甲醇洗涤1~2次,干燥得到聚(苯乙烯-二乙烯基苯)包覆纳米二氧化硅的核壳颗粒;步骤三:常温下,将聚(苯乙烯-二乙烯基苯)包覆纳米二氧化硅的核壳颗粒、交联剂和有机溶剂搅拌1~5小时,磁力搅拌0.1~2小时,然后加入作为催化剂的路易斯酸,保持磁力搅拌,升温至30~60℃,在该温度下反应2~12小时后再升温至70~120℃,在该温度下反应10~72小时,获得极粘稠固液混合物,过滤该极粘稠固液混合物,获得褐色固体,用***、甲醇洗涤该固体1~5次除去残留交联剂、溶剂和催化剂,再用甲醇抽提12~36小时以除去剩余的催化剂路易斯酸,使用氢氟酸除去纳米二氧化硅颗粒,干燥得到用于药物负载和释放、负载催化剂或离子吸附剂的高分子载体:黄褐色或紫色的多孔聚合物空心微囊。
聚苯胺作为最早发现的导电聚合物,具有低成本、易合成、高导电性、多氧化态和高赝电容等特点,被广泛应用于涂料、电池、吸波材料、传感器和导电纤维等领域。除此之外,研究发现:固体胺基吸附剂在较低CO2分压条件下,具有较高的吸附能力,且再生温度较低(小于100℃),对设备腐蚀性较小。基于CO2与氨基基团相互作用,形成氨基甲酸、氨基甲酸酯和碳酸氢盐,聚苯胺在捕获二氧化碳的应用方面有很大的潜力。因此,将聚苯胺与空心微囊复合有望得到廉价的具有电活性和比表面积的复合材料,对二氧化碳进行捕获,具有积极的社会和经济价值。
发明内容:
本发明的目的在于克服现有技术存在的缺点,寻求设计一种聚苯胺改性亲水纳米空心微囊制备方法,以解决聚苯胺材料本身无孔结构和比表面积小,以及超交联聚合物导电性差的问题。
为了实现上述目的,本发明涉及的聚苯胺改性亲水纳米空心微囊制备方法的具体工艺过程包括制备超交联空心微囊(HCP-HC)、制备磺酸化HCP-HC(S-HCP-HC)和制备PAN改性S-HCP-HC(PANI@S-HCP-HC)共三个步骤:
(1)制备HCP-HC
首先,将体积比为2:13的KH-570和乙醇组成的混合物滴入市售的SiO2纳米颗粒乙醇分散液中,反应24h,得到的产物用甲醇洗涤离心3次,真空干燥24h,得到乙烯基改性SiO2;
其中,SiO2纳米颗粒的粒径为50~300nm,乙醇:SiO2纳米颗粒的比例为25mL:1g;
再次,将十二烷基苯磺酸钠(SDBS)和NaHCO3溶解于蒸馏水中,得到水溶液,将乙烯基改性SiO2分散在乙醇中后加入到水溶液中,连续搅拌以获得稳定的乳液,在乳液中加入苯乙烯和二乙烯基苯(DVB),将温度升至85℃,逐滴入过硫酸钾(KPS)水溶液,得到SiO2@PS-DVB;
其中,SDBS:NaHCO3的质量比为3:20,蒸馏水的体积为100mL;乙烯基改性SiO2:乙醇的比例为3mg:25mL;蒸馏水:乙醇:苯乙烯的体积比为10:1:1;DVB的体积为苯乙烯的体积的2-25%;KPS水溶液的浓度为0.1g/mL;
然后,将SiO2@PS-DVB置于二氯乙烷(DCE)和二甲氧基甲烷(FDA)组成的混合液中溶胀1h,在温度为35℃的条件下,加入FeCl3,将温度升高到45℃,反应5h,将反应产物加热到80℃,保持19h,清洗过滤,得到SiO2@HCPs;
其中,SiO2@PS-DVB:DCE:FDA的比例为1g:20mL:1.73mL;FeCl3:FDA的比例为3.32g:1.73mL;
最后,用氢氟酸刻蚀SiO2@HCPs,过滤后清洗,获得棕色的HCP-HC,置于温度为60℃的真空环境中干燥24h备用;
(2)制备S-HCP-HC
在浓硫酸中搅拌加入HCP-HC,在温度为35℃的条件下搅拌4h后,小心用乙醇清洗过滤,置于温度为60℃的环境中干燥,得到S-HCP-HC;
其中,浓硫酸:HCP-HC的比例为10mL:1g;
(3)制备PANI@S-HCP-HC
将浓盐酸和苯胺混合后,加入水,室温下搅拌3h,加入S-HCP-HC搅拌6h,滴入过硫酸铵(APS)水溶液,室温下反应2h,用水和乙醇清洗过滤得到的产物,置于温度为60℃的环境中干燥,得到PANI@S-HCP-HC;
其中,S-HCP-HC:水的比例为0.2g:1mL;S-HCP-HC:苯胺的比例为1g:1-4mL;浓盐酸:苯胺的体积比为4:1;APS:苯胺的比例为0.12g:1mL,APS水溶液的体积为1mL。
本发明涉及的PANI@S-HCP-HC用于制备电化学捕获二氧化碳材料:PANI@S-HCP-HC碳捕获电极,能够提高聚苯胺的比表面积,通过控制苯胺的添加量,能够调整电化学捕获二氧化碳材料的孔径和导电性,有效促进电化学捕获二氧化碳;
具体制备工艺过程为:将PANI@S-HCP-HC和碳纳米管分散于乙醇中,得到分散液,加入聚四氟乙烯(PTFE)用作粘结剂,超声使其混合均匀,用微量移液枪滴于打磨好的玻碳电极上,置于温度为60℃的环境中干燥1h,得到PANI@S-HCP-HC碳捕获电极;其中,PTFE的质量百分比浓度为1%;PANI@S-HCP-HC:碳纳米管:PTFE的比例为4:5:1。
本发明与现有技术相比,基于聚苯胺本身具有的导电性使复合材料具有电化学活性,S-HCP-HC具有的亲水、结构可调、比表面积大、稳定性好、结构多样、价格便宜、可以负载其它金属等优点,将PANI与磺化后的HCP-HC结合,S-HCP-HC的亲水性使PANI进入到S-HCP-HC的孔结构中,使PANI@S-HCP-HC具有良好的形貌,并保持高比表面积;其原理科学可靠,工序操作简单,反应条件温和,无需特殊的反应设备和需昂贵的催化剂,生产成本低廉。
附图说明:
图1为本发明实施例制备的PANI@S-HCP-HC和S-HCP-HC的循环伏安曲线图。
具体实施方式:
下面通过实施实例并结合附图对本发明做进一步描述。
实施例1:
本实施例涉及的聚苯胺改性亲水纳米空心微囊制备方法的具体工艺过程如下:
剧烈机械搅拌500mL乙醇和40mL TEOS组成的混合液,再加入40mL NH3·H2O,搅拌24h后,得到分散液,将4mL KH-570和26mL乙醇组成的混合物滴入分散液中,反应24h后,用甲醇洗涤离心反应产物3次,真空干燥24h,得到SiO2;
将0.036g SDBS和0.24g NaHCO3溶解于100mL蒸馏水中,得到水溶液,将1.2mg SiO2分散于10mL乙醇中后,加入到水溶液中,连续搅拌以获得稳定的乳液,向乳液中加入10mL苯乙烯和体积占比为苯乙烯5%的DVB,将温度升至85℃,逐滴入1mL浓度为0.1g/mL的KPS水溶液,得到SiO2@PS-DVB;
将1g SiO2@PS-DVB置于20mL DCE和1.73mL FDA组成的混合液中溶胀1h,在温度为35℃的条件下,加入3.32g FeCl3,将温度提高至45℃,反应5h,将反应产物加热到80℃,保持19h,清洗过滤,得到SiO2@HCPs;
用氢氟酸刻蚀SiO2@HCPs,过滤后清洗,获得棕色的HCP-HC,在温度为60℃的真空环境中干燥24h;
将5mL浓硫酸搅拌加入到0.5g HCP-HC中,在温度为35℃的条件下搅拌4h后,小心用乙醇清洗过滤,在温度为60℃的条件下干燥,得到S-HCP-HC;
将0.2mL浓HCl和0.1mL苯胺混合后,加入1mL水,室温下搅拌3h,加入0.2g S-HCP-HC搅拌6h,滴入1mL 0.012g/mL APS水溶液,室温下反应2h,用水和乙醇清洗过滤得到的产物,置于温度为60℃的环境中干燥,得到PANI@S-HCP-HC。
实施例2:
本实施例涉及的PANI@S-HCP-HC制备方法的工艺过程同实施例1,不同之处在于:浓HCl的体积为0.3mL,苯胺的体积为0.07mL,APS水溶液的浓度为0.016g/mL。
实施例3:
本实施例涉及的PANI@S-HCP-HC制备方法的工艺过程同实施例1,不同之处在于:浓HCl的体积为0.4mL,苯胺的体积为0.05mL,APS水溶液的浓度为0.024g/mL。
实施例4:
实施例1、2和3制备的PANI@S-HCP-HC和S-HCP-HC制备的工作电极在100mV/s的扫描速率下,-0.2至0.8V的电势范围内的CV曲线如图1所示,与S-HCP-HC相比,PANI@S-HCP-HC的CV曲线面积有所增加,表明PANI改善了S-HCP-HC的电化学性能;PANI@S-HCP-HC表现出赝电容特性,包含两对氧化还原峰,其中A/A’归因于翠绿亚胺-青霉素苯胺的转变,B/B’归因于PANI在半导体状态和导电状态之间的氧化还原转变,CV曲线的面积随PANI的增加而增加。
Claims (10)
1.一种聚苯胺改性亲水纳米空心微囊制备方法,工艺过程包括制备超交联空心微囊、制备磺酸化HCP-HC和制备PAN改性S-HCP-HC共三个步骤,其特征在于:
(1)制备HCP-HC
首先,将KH-570和乙醇组成的混合物滴入SiO2纳米颗粒乙醇分散液中,反应,得到的产物用甲醇洗涤离心,真空干燥,得到乙烯基改性SiO2;
再次,将十二烷基苯磺酸钠和NaHCO3溶解于蒸馏水中,得到水溶液,将乙烯基改性SiO2分散在乙醇中后加入到水溶液中,连续搅拌,获得稳定的乳液,在乳液中加入苯乙烯和二乙烯基苯,升温,逐滴入过硫酸钾水溶液,得到SiO2@PS-DVB;
然后,将SiO2@PS-DVB置于二氯乙烷和二甲氧基甲烷组成的混合液中溶胀,加入FeCl3,反应,将反应产物加热,保持,清洗过滤,得到SiO2@HCPs;
最后,用氢氟酸刻蚀SiO2@HCPs,过滤后清洗,获得HCP-HC,置于真空环境中干燥;
(2)制备S-HCP-HC
在浓硫酸中搅拌加入HCP-HC,搅拌,用乙醇清洗过滤,干燥,得到S-HCP-HC;
(3)制备PANI@S-HCP-HC
将浓盐酸和苯胺混合后,加入水,搅拌,加入S-HCP-HC搅拌,滴入过硫酸铵水溶液,反应,用水和乙醇清洗过滤得到的产物,干燥,得到PANI@S-HCP-HC。
2.根据权利要求1所述的一种聚苯胺改性亲水纳米空心微囊制备方法,其特征在于,具体工艺过程如下:
(1)制备HCP-HC
首先,将体积比为2:13的KH-570和乙醇组成的混合物滴入市售的SiO2纳米颗粒乙醇分散液中,反应24h,得到的产物用甲醇洗涤离心3次,真空干燥24h,得到乙烯基改性SiO2;
再次,将十二烷基苯磺酸钠和NaHCO3溶解于蒸馏水中,得到水溶液,将乙烯基改性SiO2分散在乙醇中后加入到水溶液中,连续搅拌以获得稳定的乳液,在乳液中加入苯乙烯和二乙烯基苯,将温度升至85℃,逐滴入过硫酸钾水溶液,得到SiO2@PS-DVB;
然后,将SiO2@PS-DVB置于二氯乙烷和二甲氧基甲烷组成的混合液中溶胀1h,在温度为35℃的条件下,加入FeCl3,将温度升高到45℃,反应5h,将反应产物加热到80℃,保持19h,清洗过滤,得到SiO2@HCPs;
最后,用氢氟酸刻蚀SiO2@HCPs,过滤后清洗,获得棕色的HCP-HC,置于温度为60℃的真空环境中干燥24h备用;
(2)制备S-HCP-HC
在浓硫酸中搅拌加入HCP-HC,在温度为35℃的条件下搅拌4h后,小心用乙醇清洗过滤,置于温度为60℃的环境中干燥,得到S-HCP-HC;
(3)制备PANI@S-HCP-HC
将浓盐酸和苯胺混合后,加入水,室温下搅拌3h,加入S-HCP-HC搅拌6h,滴入过硫酸铵水溶液,室温下反应2h,用水和乙醇清洗过滤得到的产物,置于温度为60℃的环境中干燥,得到PANI@S-HCP-HC。
3.根据权利要求1或2所述的一种聚苯胺改性亲水纳米空心微囊制备方法,其特征在于,PANI@S-HCP-HC用于制备电化学捕获二氧化碳材料:PANI@S-HCP-HC碳捕获电极,通过控制苯胺的添加量,调整电化学捕获二氧化碳材料的孔径和导电性。
4.根据权利要求1或2所述的一种聚苯胺改性亲水纳米空心微囊制备方法,其特征在于,步骤(1)中,SiO2纳米颗粒的粒径为50~300nm,乙醇:SiO2纳米颗粒的比例为25mL:1g;SDBS:
NaHCO3的质量比为3:20,蒸馏水的体积为100mL;乙烯基改性SiO2:乙醇的比例为3mg:25mL;蒸馏水:乙醇:苯乙烯的体积比为10:1:1;DVB的体积为苯乙烯的体积的2-25%;KPS水溶液的浓度为0.1g/mL;SiO2@PS-DVB:DCE:FDA的比例为1g:20mL:1.73mL;FeCl3:FDA的比例为3.32g:1.73mL。
5.根据权利要求1或2所述的一种聚苯胺改性亲水纳米空心微囊制备方法,其特征在于,步骤(2)中,浓硫酸:HCP-HC的比例为10mL:1g。
6.根据权利要求1或2所述的一种聚苯胺改性亲水纳米空心微囊制备方法,其特征在于,步骤(3)中,S-HCP-HC:水的比例为0.2g:1mL;S-HCP-HC:苯胺的比例为1g:1-4mL;浓盐酸:苯胺的体积比为4:1;APS:苯胺的比例为0.12g:1mL,APS水溶液的体积为1mL。
7.根据权利要求3所述的一种聚苯胺改性亲水纳米空心微囊制备方法,其特征在于,具体制备工艺过程为:将PANI@S-HCP-HC和碳纳米管分散于乙醇中,得到分散液,加入粘结剂,超声,滴于玻碳电极上,干燥1h,得到PANI@S-HCP-HC碳捕获电极。
8.根据权利要求7所述的一种聚苯胺改性亲水纳米空心微囊制备方法,其特征在于,粘结剂为聚四氟乙烯。
9.根据权利要求7所述的一种聚苯胺改性亲水纳米空心微囊制备方法,其特征在于,置于温度为60℃的环境中干燥。
10.根据权利要求7所述的一种聚苯胺改性亲水纳米空心微囊制备方法,其特征在于,PTFE的质量百分比浓度为1%;PANI@S-HCP-HC:碳纳米管:PTFE的比例为4:5:1。
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